Pd-Catalyzed Suzuki–Miyaura Cross-Coupling of Arylboronic Acids and α-Iminonitriles through C–CN Bond Activation

Article abstract of DOI:10.1002/ejoc.201800857

A Pd-catalyzed Suzuki–Miyaura cross-coupling reaction between arylboronic acids and α-iminonitriles has been developed. The reaction proceeds through selective activation of the C–CN bond, tolerates a wide range of substituents, and delivers the versatile ketone products in moderate to excellent yields.

Full text of DOI:10.1002/ejoc.201800857

A Journal of
Accepted Article
Title: Pd-Catalyzed Suzuki−Miyaura Cross-Coupling of Arylboronic
acids and α-Iminonitriles via C-CN Bond Activation.
Authors: Yongming Zhu, Kui Liu, Shou-Wei Tao, and Chun Qian
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To be cited as: Eur. J. Org. Chem. 10.1002/ejoc.201800857
Link to VoR: http://dx.doi.org/10.1002/ejoc.201800857
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European Journal of Organic Chemistry
10.1002/ejoc.201800857
FULL PAPER
Pd-Catalyzed Suzuki−Miyaura Cross-Coupling of Arylboronic
acids and α-Iminonitriles via C-CN Bond Activation.
*
Kui Liu, Shou-Wei Tao, Chun Qian and Yong-Ming Zhu
Abstract: Pd-catalyzed Suzuki-Miyaura cross-coupling between
arylboronic acids and α-iminonitriles has been developed. The
reaction proceeds via selective activation of the C-CN bond,
tolerates a wide range of substituents and delivers the versatile
ketone products in moderate to excellent yields.
which can then be trapped by a nucleophile, followed by
hydrolysis to form the product (Scheme 1 b).
Introduction
Transition-metal-catalyzed C-CN bond activation has emerged
as powerful strategy for chemical synthesis, owing to the strong
C-CN bond (ca. 130 kcal/mol for Ar-CN) can be cleaved without
1
the aid of ring strain or extra coordinating groups and the
availability and natural abundance of aryl nitriles. In the past
decades, significant progress has been made in the
development of transformations involving C-CN bond activation,
2
3
including isomerization, cross-coupling reactions, and the
4
-8
vicinal difunctionalization of olefins. Despite these significant
advances, however, cleavage of C-CN bond of acylnitriles by
transition metals to form acyl-metal intermediates for catalytic
9
cross-coupling reactions with organometallic reagents for the
chemoselective formation of ketones is virtually unknown.
This surprising barrier of C-CN activation of acylnitriles in
synthetic chemistry is due to they have strong tendency to
Scheme 1. Metal-Catalyzed C-CN Bond Activation Reactions of α-Iminonitriles.
1
0
undergo decarbonylation after activation and the acylnitriles
Results and Discussion
o
11
decompose easily at high temperatures (greater than 100 C).
α-Iminonitriles are quite stable to high temperature and water
and cannot undergo decarbonylation, yet can yield a carbonyl
group after hydrolysis upon workup. These characteristics make
them as fantastic surrogates of acylnitriles. Seminal work by the
Initial investigations were carried out using (Z)-N-
cyclopropylbenzimidoyl cyanide 1a and phenylboronic acid 2a
as substrates in the presence of Pd(PPh
CuCl ·2H O (2 equiv), and NaOAc (2 equiv) in toluene for 24 h
under nitrogen, and the desired benzophenone was obtained in
5% yield (Table 1, entry 1). Compared with other copper
sources (Table 1, entries 2-6), Cu(TFA) was optimal for this
reaction. Increasing or decreasing the amount of Cu(TFA) were
3 4 ,
) (10% mmol)
1
1
2
2
group of Douglas showed that acylnitriles could be substituted
by α-iminonitriles, and thus achieved intramolecular
acylcyanation of alkenes (Scheme 1 a). On the other hand,
biaryl ketones are conventionally synthesized by the Friedel–
3
2
1
2
2
Crafts acylation, or palladium-catalyzed carbonylative Suzuki
reactions of aryl halides with CO serves as the carbonyl
not conducive for this reaction (Table 1, entries 8 and 9). Solvent
screening found that with the increase of the solvent polarity, by-
product 3aa (Scheme 2) also increased and cyclohexane was
clearly superior to other solvents (Table 1, entries 10-14).
13
source.
However, the reaction, which incorporates
stoichiometric amounts of a Lewis acid, suffers from poor
compatibility with functional groups and CO is toxic gas usually
used in excess and under high pressure. Therefore, it is of
considerable interest to develop a process for synthesizing diaryl
Switching to other catalysts, such as PdCl
2 2
(PPh)2, Pd(OAc) and
Pd(dba) resulted in lower yields (Table 1, entries 15-17). Other
2
commercially available bases were also tested to further
improve the yield, however, none of them were found to
compete with NaOAc (Table 1, entries 19-25). When using
K PO4, Na CO and NaHCO , the by-product 3ab (Scheme 2)
3 2 3 3
increased significantly. Without addition of the base, there is no
product (Table 1, entry 26). To determine the role of copper (II)
ketones using
a new co-catalyst. Considering the unique
properties of α-iminonitriles, we envisioned that the cross-
coupling between acylnitriles and arylboronic acids could be
realized using α-iminonitriles as precursors. This reaction is
1
1, 14
initiated by transition-metal oxidative addition to C-CN bond
to generate a unique electrophilic imide-metal intermediate,
2 2
in the reaction, we replaced Cu(TFA) by ZnCl , but only trace
product was detected (Table 1, entry 27). Lowering the
temperature did not give better result (Table 1, entry 28). It
should be noted that the benzophenone was obtained in one-pot
without additional step of hydrolysis, which made this reaction
more convenient and attractive.
[
a]
College of Pharmaceutical Sciences, Soochow University, Suzhou,
15123, China.
E-mail: zhuyongming@suda.edu.cn
2
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European Journal of Organic Chemistry
10.1002/ejoc.201800857
FULL PAPER
e
2
8
Pd(PPh
3
)
4
Cu(TFA)
2
NaOAc
cyclohexane
25
[
a] General conditions: All reactions were run on a 0.5 mmol scale under
nitrogen in solvent (2 ml) with 2a (2 equiv), catalyst (10 mol %), base (2
o
Scheme 2. By-products in the Synthetic Reaction of 3a
equiv), [Cu] in a sealed tube for 24h at 130 C. [b] Isolated yields. [c] Cu(TFA)
2
o
2
2
.5 equiv. [d] Cu(TFA) 1.5 equiv. [e] 100 C. n.d: Not detected.
a
Table 1. Optimization of Reaction Conditions
With the optimized reaction conditions in hand, we next explored
the scope of the reaction using (Z)-N-cyclopropylbenzimidoyl
cyanide 1a and various arylboronics. As illustrated in Table 2,
the reaction tolerates a wide range of aromatic boronic acids
bearing sensitive functional groups, such as cyano (3h), nitro
(
3i), aryl halides (3c, 3d and 3j), that provide synthetic handles
b
Entry
Catalyst
[Cu]
Base
Solvent
toluene
Yield(%)
35
for further functionalization. In addition, 3,4-disubstituted
aromatic boronic acids (3e and 3f) gave products in moderate to
high yields. Electron-donating (3k-3m) and electron-withdrawing
1
2
3
4
5
6
7
8
9
Pd(PPh
Pd(PPh
Pd(PPh
Pd(PPh
Pd(PPh
Pd(PPh
Pd(PPh
Pd(PPh
Pd(PPh
Pd(PPh
3
)
3
)
3
)
3
)
3
)
3
)
3
)
3
)
3
)
3
)
4
4
4
4
4
4
4
4
4
4
CuCl
2
·2H
2
O
NaOAc
NaOAc
NaOAc
NaOAc
NaOAc
NaOAc
NaOAc
NaOAc
NaOAc
NaOAc
NaOAc
NaOAc
NaOAc
NaOAc
NaOAc
NaOAc
NaOAc
NaOAc
(
(
3g) boronic acids are well-tolerated. Electron-neutral naphthyl
3b) could also be transformed into the corresponding ketone in
Cu(OH)
2
toluene
trace
62
Cu(TFA)
2
toluene
excellent yield. Steric hindrance has a slight effect on the
reaction (3n). Unfortunately, heteroaromatic boronic acids, such
as furan-2-ylboronic acid (3o) were unreactive under these
reaction conditions.
Next, we turned our attention to the scope of α-iminonitriles
using (4-chlorophenyl) boronic acid as a coupling partner (Table
Cu(OTf)
2
toluene
trace
20
Cu(OAc)
2
toluene
CuBr
-
2
toluene
n.d
3). Particularly noteworthy is the functional group tolerance of
toluene
n.d
our protocol, accommodating α-iminonitriles with different
electronic properties and substitution patterns (4a-4q). Notably,
α-iminonitriles incorporating a series of sensitive functional
groups, including benzyloxy (4d), N,N-dimethylamino (4e), and
nitro (4l), underwent cross-coupling smoothly and adducts were
isolated with high yields. Naphthyl (4g) and heteroaromatic (4h)
α-iminonitriles underwent coupling with high reaction efficiency.
Importantly, our result demonstrates that the reaction is not
limited to reactive and π-extended aromatic rings, α, β-
unsaturated α-iminonitrile (4i) was also compatible with the
method but a lower yield of the product was obtained. Sterically
differentiated α-iminonitrile (4o) revealed that steric has no effect
in the cross-coupling. All of above examples proved a variety of
functionalized α-iminonitriles that could be coupled with a range
of boronic acids to give electronically diverse products.
c
Cu(TFA)
Cu(TFA)
Cu(TFA)
Cu(TFA)
Cu(TFA)
Cu(TFA)
Cu(TFA)
Cu(TFA)
Cu(TFA)
Cu(TFA)
Cu(TFA)
Cu(TFA)
Cu(TFA)
Cu(TFA)
Cu(TFA)
Cu(TFA)
Cu(TFA)
Cu(TFA)
Cu(TFA)
2
2
2
2
2
2
2
2
2
2
2
2
2
2
2
2
2
2
2
toluene
51
d
toluene
58
1
1
1
1
1
1
1
1
1
1
2
2
2
2
2
2
2
2
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
p-xylene
60
73
Pd(PPh
3
)
4
cyclohexane
n-heptane
1,4-dioxane
THF
Pd(PPh
Pd(PPh
Pd(PPh
3
)
3
)
3
)
4
4
4
50
15
<10
<10
n.d
64
PdCl
2
(PPh)
2
cyclohexane
cyclohexane
cyclohexane
cyclohexane
cyclohexane
cyclohexane
cyclohexane
cyclohexane
cyclohexane
cyclohexane
cyclohexane
cyclohexane
cyclohexane
Pd(OAc)
2
Pd(dba)
-
2
Table 2 Boronic Acid Scope in the Pd-Catalyzed Cross-Coupling
a, b
n.d
49
of α-Iminonitriles.
Pd(PPh
Pd(PPh
Pd(PPh
Pd(PPh
Pd(PPh
Pd(PPh
Pd(PPh
Pd(PPh
Pd(PPh
3
3
3
3
3
3
3
3
3
)
4
4
4
4
4
4
4
4
4
HCO
Et
CsF
2
Na
)
)
)
)
)
)
)
)
3
N
40
30
3
K PO
4
50
Na
2
CO
3
n.d
n.d
58
NaHCO
3
NaTFA
-
n.d
trace
ZnCl
2
NaOAc
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European Journal of Organic Chemistry
10.1002/ejoc.201800857
FULL PAPER
[
2
a] Conditions: All reactions were performed under N on a 0.5 mmol
scale using 1 (0.5 mmol), 2d (2 equiv), Pd(PPh
3
)
4
(10% mmol), Cu(TFA)
2
o
(2 equiv), NaOAc (2 equiv) in cyclohexane (2ml) at 130 C for 24 h. [b]
Isolated yields. [c] Cyclohexane (3ml). [d] 2.5 equiv Cu(TFA)
2
was used.
a, b
Table 4. Pd-Catalyzed Cross-Coupling of other iminonitriles.
3
b
entry
1a
R
Yield (%)
1
2
3
1aa
1ab
1ac
t-Bu-
PhCH
-OH
60
62
12
2
2
CH -
[
a] Conditions: All reactions were performed under N
mmol scale using 1a (0.5 mmol), 2 (2 equiv), Pd(PPh
mmol), Cu(TFA) (2 equiv), NaOAc (2 equiv) in cyclohexane
2ml) at 130 C for 24 h. [b] Isolated yields.
2
on a 0.5
[
a] Conditions: All reactions were performed under N
mmol scale using 1aa (0.5 mmol), 2a (2 equiv), Pd(PPh
mmol), Cu(TFA) (2 equiv), NaOAc (2 equiv) in cyclohexane
2ml) at 130 C for 24 h. [b] Isolated yields.
2
on a 0.5
3 4
)
(10%
3 4
)
(10%
2
2
o
(
o
(
Table
3 α-Iminonitrile Scope in the Pd-Catalyzed Cross-
a, b
To further demonstrate the capability of this cross-coupling
reaction, we tested several other α-iminonitriles with 2a under
the optimized conditions, as depicted in Table 4. Using N-OH
Coupling of α-iminonitriles
(
1ac) substituted α-iminonitrile, the yield decreased drastically.
Compared with N-cyclopropyl (1a), the yield of N-tertiary butyl
(
1aa) and N-phenethyl (1ab) are slightly lower.
14, 15
On the basis of the literature reports
and experimental
results, a plausible mechanism for this reaction is depicted in
scheme 3. As neither by-product 3ab nor target product were
observed without Cu(TFA)
detected in the absence of Pd(PPh
assumed that [Cu] plays an irreplaceable role in C-CN bond
2
(Table 1, entry 7), but the 3ab was
3 4
)
(Table 1, entry 18), we
1
4
activation. Initial oxidative addition of 2a with Pd(0) generated
palladium complex A. At this point, could react with
superfluous 2a to afford 3aa. Meanwhile, C-CN bond of 1a
underwent copper-catalyzed oxidation to generate
intermediate D. On the one hand, D run into H O afforded by-
A
a
2
product 3ab (Path 3). On the other hand, transmetalation of D
with A facilitates the formation of B (Paths 1and 2). B underwent
reductive elimination delivered C, followed by hydrolysis to form
product 3a, and Pd(0) species is regenerated to complete the
catalytic cycle.
Scheme 3 Proposed mechanism.
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European Journal of Organic Chemistry
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In a 15 mL sealed tube equipped with a magnetic stirring bar were added
α-iminonitriles (0.5 mmol), arylboronic acids (2 equiv), Pd(PPh
mmol), Cu(TFA) (2 equiv), NaOAc (2 equiv) in cyclohexane (2ml). The
tube was purged with N , and the contents were stirred at 130 °C for 24 h.
3 4
) (10%
2
2
After completion of the reaction, the mixture was diluted with EtOAc then
filtered through a pad of Celite. The solvent was removed by vacuum.
The residue was purified on a silica gel column using petroleum
ether/EtOAc as the eluent to give the pure target products.
17
1
Benzophenone (3a). Oil (66 mg, 73%). H NMR (400 MHz, CDCl
3
) δ
7
.81 (d, J = 7.4 Hz, 4H), 7.59 (t, J = 7.3 Hz, 2H), 7.49 (t, J = 7.5 Hz, 4H).
13
C NMR (101 MHz, CDCl
3
) δ 196.8, 137.7, 132.5, 130.1, 128.4. HRMS
+
(ESI) m/z calcd for C13 11O [M + H] : 183.0811, found 183.0814.
H
17
Naphthalen-2-yl(phenyl)methanone (3b). White solid (84 mg, 72%).
1
H NMR (400 MHz, CDCl
3
) δ 8.27 (s, 1H), 7.95 (s, 2H), 7.92 (d, J = 8.4
Hz, 2H), 7.87 (d, J = 7.5 Hz, 2H), 7.62 (d, J = 6.7 Hz, 2H), 7.54 (dt, J =
1
3
1
1
1
5.0, 7.6 Hz, 3H). C NMR (101 MHz, CDCl
3
) δ 196.9, 138.1, 135.4,
34.9, 132.5, 132.4, 132.0, 130.2, 129.6, 128.5, 128.5, 128.4, 127.9,
26.9, 125.9. HRMS (ESI) m/z calcd for C17H13O [M + H] : 233.0967,
+
found 233.0975.
1
8
(
4-Chlorophenyl)(phenyl)methanone (3c). White solid (99 mg, 91%).
1
3
H NMR (400 MHz, CDCl ) δ 7.77 (t, J = 7.0 Hz, 4H), 7.61 (t, J = 6.6 Hz,
H), 7.48 (dd, J = 14.8, 7.8 Hz, 4H). C NMR (101 MHz, CDCl
13
1
3
) δ 195.7,
1
39.0, 137.4, 136.0, 132.8, 131.6, 130.1, 128.8, 128.6. HRMS (ESI) m/z
+
calcd for C13
H10ClO [M + H] : 217.0421, found 217.0426.
Conclusions
17
(
4-Fluorophenyl)(phenyl)methanone (3d). White solid (55 mg, 55%).
H NMR (400 MHz, CDCl
1
3
) δ 7.88 – 7.82 (m, 2H), 7.77 (d, J = 7.6 Hz,
In summary, we have reported the first cross-coupling reaction
of arylboronic acids coupled with C-CN bond activation. Using α-
iminonitriles as the surrogate for acyl nitriles successfully
avoided the side reaction of decarbonylation. Besides, the diaryl
ketones were obtained in one-pot without additional step of
hydrolysis. Characterized by wide substrate scope, moderate to
excellent yields and without the use of complex ligands or
expensive additives, this synthetic protocol may aid the further
development of the reactions incorporating C-CN bond
activation of acylnitriles.
2H), 7.60 (t, J = 7.2 Hz, 1H), 7.49 (t, J = 7.4 Hz, 2H), 7.16 (t, J = 8.2 Hz,
13
2H). C NMR (101 MHz, CDCl
3
) δ 195.4, 165.5 (d, J = 254.2 Hz), 137.6,
1
33.9 (d, J = 3.1 Hz), 132.8 (d, J = 9.1 Hz), 132.6, 130.0, 128.5, 115.6 (d,
+
J = 21.8 Hz). HRMS (ESI) m/z calcd for C13
H10FO [M + H] : 201.0716,
found 201.0723.
17
1
(
3,4-Difluorophenyl)(phenyl)methanone (3e). Oil (90 mg, 83%). H
3
NMR (400 MHz, CDCl ) δ 7.76 (d, J = 7.5 Hz, 2H), 7.72 – 7.65 (m, 1H),
7
.61 (dd, J = 15.0, 7.7 Hz, 2H), 7.50 (t, J = 7.5 Hz, 2H), 7.27 (q, J = 8.1
13
Hz, 1H). C NMR (101 MHz, CDCl
Hz), 150.3 (dd, J = 251.0, 13.0 Hz), 137.0, 135.30 – 133.85 (m), 132.9,
3
) δ 194.2, 153.4 (dd, J = 256.3, 12.8
1
1
2
29.9, 128.6, 127.2 (dd, J = 7.3, 3.7 Hz), 119.5 (dd, J = 18.1, 1.5 Hz),
+
9 2
17.4 (d, J = 17.8 Hz). HRMS (ESI) m/z calcd for C13H F O [M + H] :
19.0622, found 219.0629.
Experimental Section
2
7
(
5
3,4-Dichlorophenyl)(phenyl)methanone (3f). White solid (74 mg,
9%). H NMR (400 MHz, CDCl
General information
1
3
) δ 7.90 (s, 1H), 7.77 (d, J = 7.7 Hz, 2H),
7
.63 (t, J = 7.2 Hz, 2H), 7.57 (d, J = 7.3 Hz, 1H), 7.51 (t, J = 7.2 Hz, 2H).
α-Iminonitriles were prepared according to the literature previously
13
C NMR (101 MHz, CDCl
3
) δ 194.3, 137.4, 137.2, 136.8, 133.1, 132.0,
Cl O [M +
16
reported.
Other reactants and reagents were purchased from
130.6, 130.1, 129.2, 128.7. HRMS (ESI) m/z calcd for C13
H
9
2
commercial suppliers and used without special instructions. All solvents
were used directly without further purified. TLC was performed on silica
HSGF254 plates. Melting points were determined with a digital melting-
+
H] : 251.0031, found 251.0041.
17
1
13
Phenyl(4-(trifluoromethyl)phenyl)methanone (3g). White solid (51
mg, 41%). H NMR (400 MHz, CDCl
J = 7.6 Hz, 2H), 7.76 (d, J = 8.0 Hz, 2H), 7.63 (t, J = 7.2 Hz, 1H), 7.51 (t,
J = 7.5 Hz, 2H). C NMR (101 MHz, CDCl
point apparatus. H and C NMR spectra were obtained from a solution
1
1
13
3
) δ 7.90 (d, J = 7.9 Hz, 2H), 7.81 (d,
in CDCl
00/151MHz ( H/ C) spectrometer. High-resolution mass spectra
HRMS) analyses were carried out on chemical ionization (CI)
apparatus using time-of-flight (TOF) mass spectrometry. Infrared spectra
3
with TMS as internal standard using a 400/101 MHz ( H/ C) or
1
13
6
13
3
) δ 195.7, 140.9, 136.9, 133.9
(
a
(d, J = 32.7 Hz), 133.2, 130.3 (d, J = 3.5 Hz), 128.7, 125.5 (q, J = 3.7 Hz),
+
-
1
123.8 (d, J = 272.7 Hz). HRMS (ESI) m/z calcd for C14
H
10
F
3
O [M + H] :
were recorded on a Varian 1000FT-IR, νmax in cm .
251.0684, found 251.0692.
General Procedure for the Synthesis of Diaryl ketones.
18
1
4
-Benzoylbenzonitrile (3h). White solid (45 mg, 43%). H NMR (400
MHz, CDCl
3
) δ 7.88 (d, J = 8.1 Hz, 2H), 7.79 (dd, J = 8.0, 2.7 Hz, 4H),
13
7.65 (t, J = 7.3 Hz, 1H), 7.52 (t, J = 7.6 Hz, 2H). C NMR (101 MHz,
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European Journal of Organic Chemistry
10.1002/ejoc.201800857
FULL PAPER
CDCl
3
) δ 195.2, 141.4, 136.5, 133.5, 132.3, 130.4, 130.2, 128.8, 118.2,
7.71 (d, J = 8.0 Hz, 2H), 7.45 (d, J = 8.0 Hz, 2H), 6.97 (d, J = 8.3 Hz, 2H),
3.89 (s, 3H). C NMR (101 MHz, CDCl ) δ 194.4, 163.5, 138.4, 136.7,
3
+
13
115.8. HRMS (ESI) m/z calcd for C14
H10NO [M + H] : 208.0763, found
208.0772.
132.6, 131.3, 129.9, 128.7, 113.8, 55.7. HRMS (ESI) m/z calcd for
C H12ClO [M + H] : 247.0527, found 247.0533.
14 2
+
1
8
1
(
3-Nitrophenyl)(phenyl)methanone (3i). White solid (58 mg, 51%). H
NMR (400 MHz, CDCl ) δ 8.62 (s, 1H), 8.45 (d, J = 8.1 Hz, 1H), 8.15 (d,
J = 7.6 Hz, 1H), 7.81 (d, J = 7.7 Hz, 2H), 7.71 (t, J = 8.0 Hz, 1H), 7.65 (d,
3
(4-(Benzyloxy)phenyl)(4-chlorophenyl)methanone (4d). White solid
o
1
(92 mg, 57%). MP: 143-146 C. H NMR (400 MHz, CDCl
3
) δ 7.80 (d, J =
1
3
3
J = 7.2 Hz, 1H), 7.54 (t, J = 7.5 Hz, 2H). C NMR (101 MHz, CDCl ) δ
8.5 Hz, 2H), 7.71 (d, J = 8.2 Hz, 2H), 7.48 – 7.34 (m, 7H), 7.05 (d, J = 8.6
1
3
1
1
2
94.3, 148.2, 139.2, 136.4, 135.6, 133.5, 130.1, 129.8, 128.9, 126.9,
Hz, 2H), 5.16 (s, 2H). C NMR (101 MHz, CDCl
3
) δ 194.4, 162.7, 138.4,
+
24.9. HRMS (ESI) m/z calcd for C13
H
10NO
3
[M + H] : 228.0661, found
136.6, 136.3, 132.6, 131.3, 130.1, 128.9, 128.7, 128.4, 127.6, 114.7,
70.3. IR : ν (cm ) 3065, 2922, 1599, 1586, 1285, 1009, 757, 692. HRMS
-
1
28.0668.
+
(
2
ESI) m/z calcd for C20H16ClO [M + H] : 323.0840, found 323.0849.
22
1
(
3-Chlorophenyl)(phenyl)methanone (3j). Oil (56 mg, 52%). H NMR
(
400 MHz, CDCl
3
) δ 7.79 (d, J = 7.8 Hz, 3H), 7.67 (d, J = 7.6 Hz, 1H),
(4-Chlorophenyl)(4-(dimethylamino)phenyl)methanone (4e). White
o
1
7
7
1
.62 (t, J = 7.3 Hz, 1H), 7.56 (d, J = 8.0 Hz, 1H), 7.50 (t, J = 7.5 Hz, 2H),
.43 (t, J = 7.8 Hz, 1H). C NMR (101 MHz, CDCl
37.1, 134.7, 132.9, 132.5, 130.2, 130.0, 129.8, 128.6, 128.2. HRMS
solid (55 mg, 42%). MP: 119-121 C. H NMR (400 MHz, CDCl
3
) δ 7.76 (d,
13
3
) δ 195.4, 139.4,
J = 8.8 Hz, 2H), 7.67 (d, J = 8.3 Hz, 2H), 7.43 (d, J = 8.3 Hz, 2H), 6.69 (d,
1
3
J = 8.8 Hz, 2H), 3.08 (s, 6H). C NMR (151 MHz, CDCl
137.7, 137.5, 132.8, 131.0, 128.4, 124.5, 110.7, 40.2. IR: ν (cm ) 2919,
851, 2809, 1601, 1524, 1286, 1196, 925, 759, 674. HRMS (ESI) m/z
3
) δ 193.9, 153.5,
+
-1
(ESI) m/z calcd for C13H10ClO [M + H] : 217.0421, found 217.0428.
2
+
17
1
calcd for C15H15ClNO [M + H] : 260.0843, found 260.0850.
Phenyl(p-tolyl)methanone (3k). Oil (59 mg, 60%). H NMR (400 MHz,
CDCl ) δ 7.77 (d, J = 7.6 Hz, 2H), 7.71 (d, J = 7.8 Hz, 2H), 7.56 (t, J = 7.2
Hz, 1H), 7.46 (t, J = 7.4 Hz, 2H), 7.29 – 7.24 (m, 2H), 2.43 (s, 3H).
NMR (151 MHz, CDCl ) δ 196.7, 143.4, 138.1, 135.0, 132.3, 130.4,
1
1
3
13
21
C
(4-Chlorophenyl)(3,4,5-trimethoxyphenyl)methanone (4f).
White
1
3
solid (88 mg, 58%). H NMR (400 MHz, CDCl
7.47 (d, J = 8.0 Hz, 2H), 7.02 (s, 2H), 3.94 (s, 3H), 3.87 (s, 6H). C NMR
(151 MHz, CDCl ) δ 194.7, 153.1, 142.4, 138.9, 136.3, 132.4, 131.4,
3
) δ 7.75 (d, J = 8.0 Hz, 2H),
+
13
30.1, 129.1, 128.3, 21.8. HRMS (ESI) m/z calcd for C14
97.0967, found 197.0975.
H13O [M + H] :
3
+
128.8, 107.8, 61.1, 56.5. HRMS (ESI) m/z calcd for C16
4
H16ClO [M + H] :
1
7
1
3
07.0738, found 307.0746.
Phenyl(m-tolyl)methanone (3l). Oil (89 mg, 91%). H NMR (400 MHz,
CDCl ) δ 7.80 (d, J = 7.1 Hz, 2H), 7.63 (s, 1H), 7.58 (d, J = 6.7 Hz, 2H),
.48 (t, J = 7.1 Hz, 2H), 7.43 – 7.35 (m, 2H), 2.42 (s, 3H). C NMR (151
MHz, CDCl ) δ 197.1, 138.3, 137.9, 137.8, 133.3, 132.5, 130.6, 130.2,
3
13
20
7
(4-Chlorophenyl)(naphthalen-2-yl)methanone (4g). White solid (101
mg, 76%). H NMR (400 MHz, CDCl
7.82 (d, J = 8.3 Hz, 2H), 7.63 (t, J = 7.4 Hz, 1H), 7.57 (t, J = 7.4 Hz, 1H),
7.50 (d, J = 8.3 Hz, 2H). C NMR (101 MHz, CDCl
1
3
3
) δ 8.23 (s, 1H), 7.96 – 7.88 (m, 4H),
+
1
28.4, 128.2, 127.5, 21.5. HRMS (ESI) m/z calcd for C14
H13O [M + H] :
13
197.0967, found 197.0972.
3
) δ 195.6, 138.9,
1
1
2
36.3, 135.5, 134.6, 132.4, 131.9, 131.6, 129.5, 128.8, 128.6, 128.6,
+
1
7
1
27.9, 127.1, 125.7. HRMS (ESI) m/z calcd for C17H12ClO [M + H] :
(
3-Methoxyphenyl)(phenyl)methanone (3m). Oil (77 mg, 73%).
H
67.0577, found 267.0583.
NMR (400 MHz, CDCl
3
) δ 7.81 (d, J = 7.3 Hz, 2H), 7.59 (t, J = 7.0 Hz,
H), 7.48 (t, J = 7.3 Hz, 2H), 7.36 (t, J = 6.1 Hz, 3H), 7.13 (d, J = 6.6 Hz,
1
1
1
13
19
H), 3.86 (s, 3H). C NMR (101 MHz, CDCl
3
) δ 196.6, 159.7, 139.0,
(4-Chlorophenyl)(furan-2-yl)methanone (4h). White solid (66 mg,
64%). H NMR (400 MHz, CDCl
1
37.7, 132.5, 130.1, 129.3, 128.4, 122.9, 118.9, 114.4, 55.6. HRMS (ESI)
m/z calcd for C14H O [M + H] : 213.0916, found 213.0926.
13 2
3
) δ 7.95 (d, J = 8.3 Hz, 2H), 7.71 (s, 1H),
+
7.47 (d, J = 8.3 Hz, 2H), 7.26 (d, J = 3.0 Hz, 1H), 6.61 (d, J = 1.5 Hz, 1H).
13
3
C NMR (101 MHz, CDCl ) δ 181.2, 152.3, 147.3, 139.2, 135.6, 130.9,
+
17
1
128.9, 120.7, 112.5. HRMS (ESI) m/z calcd for C11
8 2
H ClO [M + H] :
Phenyl(o-tolyl)methanone (3n). Oil (41 mg, 42%). H NMR (400 MHz,
CDCl ) δ 7.80 (d, J = 7.4 Hz, 2H), 7.58 (t, J = 7.3 Hz, 1H), 7.45 (t, J = 7.4
Hz, 2H), 7.39 (t, J = 7.3 Hz, 1H), 7.30 (t, J = 8.2 Hz, 2H), 7.25 (d, J = 6.6
Hz, 1H), 2.33 (s, 3H). C NMR (101 MHz, CDCl ) δ 198.7, 138.7, 137.8,
36.8, 133.2, 131.1, 130.3, 130.2, 128.6, 128.5, 125.3, 20.1. HRMS (ESI)
207.0214, found 207.0222.
3
13
26
3
(E)-1-(4-Chlorophenyl)-3-phenylprop-2-en-1-one (4i). White solid (42
mg, 35%). H NMR (400 MHz, CDCl
J = 15.7 Hz, 1H), 7.65 (s, 2H), 7.52 – 7.46 (m, 3H), 7.43 (d, J = 2.7 Hz,
1
1
3
) δ 7.97 (d, J = 8.3 Hz, 2H), 7.82 (d,
+
m/z calcd for C14
H
13O [M + H] : 197.0967, found 197.0977.
13
3H). C NMR (151 MHz, CDCl
3
) δ 189.3, 145.5, 139.3, 136.6, 134.8,
1
9
1
30.8, 130.0, 129.1, 129.1, 128.6, 121.6. HRMS (ESI) m/z calcd for
(
4-Chlorophenyl)(p-tolyl)methanone (4a). White solid (83 mg, 72%).
+
1
15 12
C H ClO [M + H] : 243.0577, found 243.0583.
H NMR (400 MHz, CDCl
3
) δ 7.73 (d, J = 8.3 Hz, 2H), 7.69 (d, J = 7.9 Hz,
H), 7.45 (d, J = 8.3 Hz, 2H), 7.29 (d, J = 7.8 Hz, 2H), 2.44 (s, 3H).
) δ 195.4, 143.7, 138.7, 136.4, 134.7, 131.5,
30.3, 129.2, 128.7, 21.8. HRMS (ESI) m/z calcd for C14
13
2
C
20
NMR (101 MHz, CDCl
1
2
3
(4-Chlorophenyl)(4-fluorophenyl)methanone (4j). White solid (88 mg,
+
1
H
12ClO [M + H] :
75%). H NMR (400 MHz, CDCl
J = 8.3 Hz, 2H), 7.47 (d, J = 8.3 Hz, 2H), 7.17 (t, J = 8.5 Hz, 2H).
NMR (101 MHz, CDCl ) δ 194.2, 165.6 (d, J = 254.6 Hz), 139.1, 135.9,
33.6 (d, J = 3.1 Hz), 132.7 (d, J = 9.2 Hz), 131.4, 128.9, 115.8 (d, J =
3
) δ 7.82 (dd, J = 8.1, 5.7 Hz, 2H), 7.73 (d,
13
31.0577, found 231.0585.
C
3
20
1
(
4-(tert-Butyl)phenyl)(4-chlorophenyl)methanone (4b). White solid
+
1
21.9 Hz). HRMS (ESI) m/z calcd for C H ClFO [M + H] : 235.0327,
found 235.0336.
(124 mg, 91%). H NMR (400 MHz, CDCl
3
) δ 7.76 (d, J = 8.8 Hz, 2H),
13 19
7
9
1
.72 (s, 2H), 7.50 (d, J = 8.1 Hz, 2H), 7.45 (d, J = 8.0 Hz, 2H), 1.37 (s,
3
) δ 195.3, 156.6, 138.7, 136.3, 134.6,
31.5, 130.1, 128.7, 125.5, 35.3, 31.3. HRMS (ESI) m/z calcd for
13
H). C NMR (101 MHz, CDCl
19
1
bis(4-Chlorophenyl)methanone (4k). White solid (119 mg, 95%).
NMR (400 MHz, CDCl ) δ 7.73 (d, J = 8.3 Hz, 4H), 7.47 (d, J = 8.3 Hz,
H). C NMR (101 MHz, CDCl ) δ 194.4, 139.3, 135.6, 131.5, 128.9.
H
+
C
17
H
18ClO [M + H] : 273.1047, found 273.1057.
3
13
4
3
+
19
HRMS (ESI) m/z calcd for C13
251.0038.
9 2
H Cl O [M + H] : 251.0031, found
(
(
4-Chlorophenyl)(4-methoxyphenyl)methanone (4c).
White solid
1
103 mg, 84%). H NMR (400 MHz, CDCl ) δ 7.80 (d, J = 8.3 Hz, 2H),
3
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European Journal of Organic Chemistry
10.1002/ejoc.201800857
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1
9
(
7
8
4-Chlorophenyl)(4-nitrophenyl)methanone (4l). White solid (98 mg,
Tooke, A. L. Spek, D. Vogt, Organometallics, 2005, 24, 13-15; d) A.
Acosta-Ramírez, A. Flores-Gaspar, M. Munōz-Hernández, A. Arévalo,
W. D. Jones, J. J. García, Organometallics, 2007, 26, 1712-1720; e) A.
Acosta-Ramírez, M. Munōz-Hernández, W. D. Jones, J. J. García,
Organometallics, 2007, 26, 5766-5769; f) A. Acosta-Ramírez, M.
Flores-Alamo, W. D. Jones, J. J. García, Organometallics, 2008, 27,
1
5%). H NMR (400 MHz, CDCl
.5 Hz, 2H), 7.76 (d, J = 8.3 Hz, 2H), 7.51 (d, J = 8.3 Hz, 2H). C NMR
) δ 193.7, 150.1, 142.6, 140.3, 134.7, 131.6, 130.7,
3
) δ 8.35 (d, J = 8.5 Hz, 2H), 7.91 (d, J =
13
(101 MHz, CDCl
3
+
1
9 3
29.2, 123.8. HRMS (ESI) m/z calcd for C13H ClNO [M + H] : 262.0272
found 262.0274.
1834-1840.
2
2
[3]
a) J. A. Miller, Tetrahedron Lett., 2001, 42, 6991-6993; b) J. A. Miller, J.
W. Dankwardt, Tetrahedron Lett., 2003, 44, 1907-1910; c) J. A. Miller, J.
W. Dankwardt, J. M. Penney, Synthesis, 2003, 11, 1643-1648; d) J. M.
Penney, J. A. Miller, Tetrahedron Lett., 2004, 45, 4989-4992.
(
3-Chlorophenyl)(4-chlorophenyl)methanone (4m). White solid (79
1
mg, 63%). H NMR (400 MHz, CDCl
J = 7.6 Hz, 1H), 7.57 (d, J = 8.1 Hz, 1H), 7.51 – 7.41 (m, 3H). C NMR
101 MHz, CDCl ) δ 194.2, 139.5, 139.0, 135.4, 134.9, 132.7, 131.5,
29.9, 129.9, 128.9, 128.1. HRMS (ESI) m/z calcd for C13 Cl O [M +
3
) δ 7.74 (d, J = 7.7 Hz, 3H), 7.64 (d,
13
(
1
3
[
[
4] a) Y. Nakao, S. Oda, T. Hiyama, J. Am. Chem. Soc., 2004, 126, 13904-
13905; b) Y. Nakao, T. Yukawa, Y. Hirata, S. Oda, J. Satoh, T. Hiyama,
J. Am. Chem. Soc., 2006, 128, 7116-7117; c) Y. Nakao, A. Yada, J.
Satoh, S. Ebata, S. Oda, T. Hiyama, Chemistry Letters, 2006, 35, 790-
791.
H
9
2
+
H] : 251.0031, found 251.0037.
(
4-Chlorophenyl)(3,5-difluorophenyl)methanone (4n). White solid (68
3
) δ 7.75 (d, J = 8.4
Hz, 2H), 7.49 (d, J = 8.4 Hz, 2H), 7.28 (d, J = 5.5 Hz, 2H), 7.05 (t, J = 8.5
3
) δ 192.8, 162.9 (dd, J = 251.6, 11.7
Hz), 140.3 (t, J = 7.6 Hz), 139.9, 134.8, 131.5, 129.1, 112.9 (dd, J = 20.8,
.5 Hz), 108.1 (t, J = 25.3 Hz). IR: ν (cm ) 3088, 2925, 1654, 1583, 1318,
o
1
mg, 54%). MP: 108-120 C. H NMR (400 MHz, CDCl
5] a) Y. Nakao, S. Ebata, A. Yada, T. Hiyama, M. Ikawa, S. Ogoshi, J. Am.
Chem. Soc., 2008, 130, 12874-12875; b) M. P. Watson, E. N. Jacobsen,
J. Am. Chem. Soc., 2008, 130, 12594-12595.
13
Hz, 1H). C NMR (151 MHz, CDCl
-
1
[6]
a) Y. Kobayashi, H. Kamisaki, R. Yanada, Y. Takemoto, Org. Lett., 2006,
8, 2711-2713; b) Y. Yasui, H. Kamisaki, Y. Takemoto, Org. Lett., 2008,
5
1
2
+
125, 983, 754. HRMS (ESI) m/z calcd for C13
8 2
H ClF O [M + H] :
1
0, 3303-3306.
7] a) Y. Nishihara, Y. Inoue, M. Itazaki, K. Takagi, Org. Lett., 2005, 7, 2639-
641; b) Y. Hirata, A. Yada, E. Morita, Y. Nakao, T. Hiyama, M. Ohashi,
53.0232, found 253.0239.
[
[
2
23
(
2-Chlorophenyl)(4-chlorophenyl)methanone (4o). White solid (88
S. Ogoshi, J. Am. Chem. Soc., 2010, 132, 10070-10077; c) N. R.
Rondla, S. M. Levi, J. M. Ryss, R. A. Vanden Berg, C. J. Douglas, Org.
Lett., 2011, 13, 1940-1943.
1
mg, 70%). H NMR (400 MHz, CDCl
7.2 Hz, 1H), 7.50 (d, J = 7.6 Hz, 1H), 7.46 (d, J = 8.2 Hz, 2H). C NMR
151 MHz, CDCl ) δ 195.6, 139.0, 137.4, 136.1, 132.8, 131.6, 130.1,
3
) δ 7.77 (t, J = 7.1 Hz, 4H), 7.60 (t, J
13
=
(
1
3
8] Recently metal catalyzed O-CN and N-CN bond activations have also
been reported: alkene oxycyanation: a) D. C. Koester, M. Kobayashi, D.
B. Werz, Y. Nakao, J. Am. Chem. Soc., 2012, 134, 6544-6547; nitrile
transfer: b) R. Wang, J. R. Falck, Chem. Commun., 2013, 49, 6516-
+
9 2
28.8, 128.5. HRMS (ESI) m/z calcd for C13H Cl O [M + H] : 251.0031,
found 251.0034.
4-Chlorophenyl)(4-(trifluoromethyl)phenyl)methanone (4p). White
24
(
6518; alkene aminocyanation: c) Y. Miyazaki, N. Ohta, K. Semba, Y.
1
3
solid (96 mg, 68%). H NMR (400 MHz, CDCl ) δ 7.87 (d, J = 8.0 Hz, 2H),
Nakao, J. Am. Chem. Soc., 2014, 136, 3732-3735; d) Z. D. Pan, S. Y.
Wang, J. T. Brethorst, C. J. Douglas, J. Am. Chem. Soc., 2018, 140,
1
3
7
.77 (s, 2H), 7.75 (s, 2H), 7.49 (d, J = 8.4 Hz, 2H). C NMR (151 MHz,
3
CDCl ) δ 194.4, 145.8, 140.5, 139.8, 135.2, 134.1 (d, J = 32.7 Hz), 131.6,
3
331–3338; alkene aminocyanation without transistion metals: d) Z.
Pan, S. M. Pound, N. R. Rondla, C. J. Douglas, Angew. Chem. Int. Ed.,
014, 53, 5170–5174.
1
30.2, 129.1, 125.6 (dd, J = 7.0, 3.4 Hz). HRMS (ESI) m/z calcd for
+
14 9 3
C H ClF O [M + H] : 285.0295, found 285.0299.
2
[
9]
a) G. R. Meng, M. Szostak, Org. Lett., 2015,17, 4364–4367; b) G. R.
Meng, S. C. Shi, M. Szostak. Synlett, 2016, 27, 2530-2540; c) C. W. Liu,
M. Szostak Chem. Eur. J., 2017, 23, 7157-7173.
2
5
[
1,1'-Biphenyl]-4-yl(4-chlorophenyl)methanone (4q). White solid (83
1
mg, 57%). H NMR (400 MHz, CDCl
3
) δ 7.87 (d, J = 8.0 Hz, 2H), 7.79 (d,
J = 8.2 Hz, 2H), 7.72 (d, J = 8.0 Hz, 2H), 7.65 (d, J = 7.5 Hz, 2H), 7.49 (t,
[10] a) S. Murahashi, T. Naota, N. Nakajima, J. Org. Chem., 1986, 51, 898-
901; b) A. Chatupheeraphat, H. H. Liao, S. C. Lee, M. Rueping, Org.
Lett., 2017, 19, 4255-4258.
13
J = 6.8 Hz, 4H), 7.42 (t, J = 7.2 Hz, 1H). C NMR (101 MHz, CDCl
3
) δ
1
1
2
95.2, 145.6, 139.9, 138.9, 136.2, 136.0, 131.5, 130.7, 129.1, 128.8,
+
28.4, 127.4, 127.2. HRMS (ESI) m/z calcd for C19H14ClO [M + H] :
[11] N. R. Rondla, J. M. Ogilvie, Z. D. Pan, C. J. Douglas, Chem. Commun.,
2014, 50, 8974-8977.
93.0734, found 293.0741.
[
[
[
12] P. H. Gore, Chem. Rev., 1955, 55, 229–281.
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RSC Adv., 2016, 6, 64234-64238. b) D. S. Marlin, M. M. Olmstead, P. K.
Mascharak, Angew. Chem.,Int. Ed., 2001, 40, 4752-4754; c) T. Lu, X.
Zhuang, Y. Li, S. Chen, J. Am. Chem. Soc., 2004, 126, 4760-4761. d) Y.
L. Shi, Q. Yuan, Z. B. Chen, F. L. Zhang, K. Liu. Synlett, 2018, 29, 359-
Acknowledgements
This work was supported by the PAPD (A Project Funded by the
Priority Academic Program Development of Jiangsu Higher
Education Institutions).
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Keywords: Cross-Coupling • C-CN Bond Activation • diaryl
1
509-1512.
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2
[
[
[
1]
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M. Tobisu, N. Chatani, Chem. Soc. Rev., 2008, 37, 300-307.
3
a) A. Chaumonnot, F. Lamy, S. Sabo-Etienne, B. Donnadieu, B.
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[
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European Journal of Organic Chemistry
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FULL PAPER
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22] X. H. Zeng, D. Q. Xu, C. X. Miao, C. G. Xia, W. Sun, RSC Adv., 2014, 4,
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[
2
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European Journal of Organic Chemistry
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Pd-Catalyzed Suzuki−Miyaura Cross-
Coupling of Arylboronic acids and α-
A valuable Pd-catalyzed Suzuki-Miyaura cross-coupling of arylboronic acids has
been developed by using α-iminonitriles to replace acylnitriles. The reaction
proceeds via selective activation of the C-CN bond and avoids the side reaction
Iminonitriles
Activation.
via
C-CN
Bond
“
decarbonylation”of acylnitriles after activation.
C-CN Bond Activation
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